CN101139111A - Monohydrated mangnese sulfate pyrolysizing process for producing mangness dioxide - Google Patents
Monohydrated mangnese sulfate pyrolysizing process for producing mangness dioxide Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 35
- 230000008569 process Effects 0.000 title claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 title 1
- 239000011572 manganese Substances 0.000 claims abstract description 44
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 38
- 239000000126 substance Substances 0.000 claims abstract description 34
- 238000007323 disproportionation reaction Methods 0.000 claims abstract description 33
- 238000000197 pyrolysis Methods 0.000 claims abstract description 26
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims abstract description 22
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 20
- 238000005406 washing Methods 0.000 claims abstract description 16
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 15
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims abstract description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229940099596 manganese sulfate Drugs 0.000 claims abstract description 10
- 235000007079 manganese sulphate Nutrition 0.000 claims abstract description 10
- 239000011702 manganese sulphate Substances 0.000 claims abstract description 10
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 10
- 239000001301 oxygen Substances 0.000 claims abstract description 10
- 238000005554 pickling Methods 0.000 claims abstract description 10
- 238000002425 crystallisation Methods 0.000 claims abstract description 4
- 230000008025 crystallization Effects 0.000 claims abstract description 4
- 238000006479 redox reaction Methods 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 30
- ISPYRSDWRDQNSW-UHFFFAOYSA-L manganese(II) sulfate monohydrate Chemical compound O.[Mn+2].[O-]S([O-])(=O)=O ISPYRSDWRDQNSW-UHFFFAOYSA-L 0.000 claims description 28
- 239000007788 liquid Substances 0.000 claims description 16
- 230000003647 oxidation Effects 0.000 claims description 15
- 230000001590 oxidative effect Effects 0.000 claims description 15
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 12
- 230000035484 reaction time Effects 0.000 claims description 11
- 230000003252 repetitive effect Effects 0.000 claims description 8
- 238000005201 scrubbing Methods 0.000 claims description 8
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 238000002242 deionisation method Methods 0.000 claims description 6
- 238000001514 detection method Methods 0.000 claims description 6
- 239000006210 lotion Substances 0.000 claims description 6
- 235000017550 sodium carbonate Nutrition 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- 239000008234 soft water Substances 0.000 claims description 6
- 230000018044 dehydration Effects 0.000 claims description 4
- 238000006297 dehydration reaction Methods 0.000 claims description 4
- 239000007800 oxidant agent Substances 0.000 claims description 3
- 238000007670 refining Methods 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 abstract description 30
- 238000004519 manufacturing process Methods 0.000 abstract description 20
- 239000000843 powder Substances 0.000 abstract description 8
- 238000001035 drying Methods 0.000 abstract description 7
- 230000006872 improvement Effects 0.000 abstract description 3
- 239000012535 impurity Substances 0.000 abstract description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract 2
- 229910052500 inorganic mineral Inorganic materials 0.000 abstract 1
- 229910052742 iron Inorganic materials 0.000 abstract 1
- BZDIAFGKSAYYFC-UHFFFAOYSA-N manganese;hydrate Chemical compound O.[Mn] BZDIAFGKSAYYFC-UHFFFAOYSA-N 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- 239000011707 mineral Substances 0.000 abstract 1
- 235000010755 mineral Nutrition 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 abstract 1
- 238000011085 pressure filtration Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 30
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 238000003756 stirring Methods 0.000 description 9
- 239000002253 acid Substances 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000001117 sulphuric acid Substances 0.000 description 5
- 235000011149 sulphuric acid Nutrition 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 239000012452 mother liquor Substances 0.000 description 4
- 239000002893 slag Substances 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
- 238000003912 environmental pollution Methods 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 230000005484 gravity Effects 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- 230000000007 visual effect Effects 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- ANFIEGWCRSNVFS-UHFFFAOYSA-N [Na].OCl(=O)=O Chemical compound [Na].OCl(=O)=O ANFIEGWCRSNVFS-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
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- Battery Electrode And Active Subsutance (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The present invention relates to a method to produce chemical manganese dioxide by water manganese sulfate pyrolysis including the technics steps of mineral powder roasting, disproportionation reaction, iron removing, manganese sulfate solution preparation, pressure crystallization, dewatering roasting, pyrolysis, redox, disproportionation.oxidation reaction, pickling, repeat washing, neutralization, pressure filtration and drying, etc. The trimanganese tetroxide after pyrolysis is pumped in the oxygen-enriched air with an oxygen content of 60 to 50 percent during redox reaction to lead part of the trimanganese tetroxide to be directly reduced to rough manganese dioxide with the manganese dioxide of more than 75 percent and lead the content of the r-shaped structure of the crystalline structure in manganese dioxide products to be improved from 75 percent to 98 percent, reduce the specific surface of the products and improve the heavy current discharge performance. Through the improvement on the technical skill, the chemical manganese dioxide produced by the present invention has become superior materials to produce alkaline manganese dry cells. The main content of the products produced by the present invention has been improved from 92 percent to 95 to 95.5 percent and the content of impurities has been reduced in large scale. The present invention is suitable for alkaline manganese cell production.
Description
Technical field
The present invention relates to the production method of the chemical manganese bioxide of chemical field, specially refer to the method that chemical manganese bioxide is produced in the manganese sulfate monohydrate pyrolysis.
Background technology
Manganse Dioxide is the main positive electrode material of drying battery, and its quality quality plays decisive role to the performance of zinc-manganse dioxide dry cell.The Manganse Dioxide that makes with electrolytic process can satisfy the specification of quality of heavy body high power battery raw material, shortcomings such as regrettably the electrolytic process preparing manganese dioxide has the power consumption height, environmental pollution is big, facility investment is big, the production cycle is long, production cost height, cause valuable product, restricted the development of battery industry to a certain extent.Eighties of last century is since the seventies, and countries in the world active development chemical manganese bioxide is produced, and the most representative have a Belgian Saden horse company, and it produces chemical manganese bioxide with ammonium ammonium formiate method, and annual production reaches 40,000 tons, the production history in existing more than 20 year.Other also has the production of small dimension as Japan, the U.S., France.The chemical manganese bioxide that this method is produced and the Chemical Composition and crystalline structure (mainly all the being the r-type) basically identical of electrolytic manganese dioxide, do not exist together is physicals, the median size of electrolytic manganese dioxide is than the big twice of chemical manganese bioxide, and specific surface has only chemical manganese bioxide half, therefore chemical manganese bioxide is compared with electrolytic manganese dioxide, has Manganse Dioxide utilization ratio height, liquid absorption is big, the battery recovery performance is strong, advantages such as anti-leakage is good, shortcoming is that (being example with Belgian) chemical manganese bioxide internal resistance is bigger, short-circuit current and load voltage are low slightly, big electric current, heavy loading discharge property is lower than electrolytic manganese dioxide slightly, and facility investment is big, production cycle is long, the production cost height, and quality product can't guarantee (to follow compression process because of ammonia is arranged, whole process of production needs High Temperature High Pressure, restive every technic index).
For addressing the above problem, the applicant has applied for " method of chemical manganese bioxide is produced in the manganese sulfate monohydrate pyrolysis " patent of invention on September 30th, 1999, it is to adopt behind the manganese sulfate monohydrate pyrolysis generation trimanganese tetroxide, be manganic oxide with the trimanganese tetroxide redox again, then with manganic oxide through disproportionation, oxidizing reaction, pickling, washing, in and technology such as press filtration oven dry make chemical manganese bioxide, it is when crystallizing into manganese sulfate monohydrate with the POV manganese solution, what adopt is pressure crystalline method: pressing force pot total volume 80% adds the POV manganese solution, heating, stir, after pressure reached 2-5kg, constant voltage was after 1 hour, open filter tap, clear liquid is put, stopped to stir, cut off electrothermal tube power, the opening pressure pot, product is poured out, through centrifugal, deposited in material-stored pool again, sampling analysis is baked to standard water-content below 3% after qualified.This method has that environmental pollution is little, and facility investment is few, (can go out product in three days) with short production cycle, production cost is low, and (because of no ammonia follows compression process, whole process of production need not High Temperature High Pressure to stable and reliable product quality, be easy to control every technic index, be convenient to the operation) etc. advantage.But along with scientific technological advance, the drying battery industry is modified into alkaline Mn cell by original acid battery.And the chemical manganese bioxide that this method is produced is not suitable for the production alkaline Mn cell, thereby partly technology must be improved.
Summary of the invention
The objective of the invention is to overcome the above-mentioned deficiency of prior art and provide a kind of facility investment few, with short production cycle, stable and reliable product quality, electrical property is better than electrolytic manganese dioxide, is applicable to the method for the manganese sulfate monohydrate pyrolysis production chemical manganese bioxide of producing alkaline Mn cell.
Technical scheme of the present invention is: the method that chemical manganese bioxide is produced in the manganese sulfate monohydrate pyrolysis comprises the breeze roasting, disproportionation, deironing, manganese sulfate solution is refining, the pressure crystallization, the dehydration roasting, pyrolysis, redox, disproportionation. oxidizing reaction, pickling, repetitive scrubbing, neutralization, processing steps such as press filtration oven dry, the trimanganese tetroxide that it is characterized in that generating after the pyrolysis is when redox reaction, feeding oxygen level is the oxygen-rich air of 60-50%, oxidization time is 2.5-6 hour, the direct oxidation of part trimanganese tetroxide is reduced into contains the thick Manganse Dioxide of Manganse Dioxide more than 75%, can reduce oxygenant chloric acid sodium consumption 30%, make the crystalline structure in the manganese dioxide product bring up to 98% by original 75% for the content of " r " type structure, increase the micropore of product particle, the aperture, reduce specific surface area, improve the product heavy-current discharge performance.
The further technical scheme of the present invention is: at disproportionation. in the oxidation reaction process, solid-to-liquid ratio must be controlled at 1 during each disproportionation reaction: 2-3, but after disproportionation reaction is finished, when adding the sodium chlorate oxidation, should solid-to-liquid ratio be reduced to 1 along with the reaction times prolongation: 1.5-2.5 is controlled at 24-30m with the specific surface area of reduction product and with it
2/ g scope improves bulk specific gravity and it is controlled in the 1.65-1.75g/ml scope raising product fill-up, thereby raising drying battery discharge capacity.
The present invention further technical scheme is: at disproportionation. in the process of oxidizing reaction, when each oxidizer is carried out oxidizing reaction, the reaction times of oxidizing reaction was controlled at 3.1-6 hour, manganous sulfate content in the while detection reaction solution, it is strict controlled in below the 10g/L, brings product into to have prevented manganic oxide.
The present invention more further technical scheme be: when repetitive scrubbing, the washing lotion pH value is washed between the 2.0-2.5 again with the yellow soda ash neutralization, and, is applicable to alkaline Mn cell to prevent the product tape ammonium ion without the bicarbonate of ammonia neutralization; After neutralization finishes, with the washing of deionization soft water, impurity in the planar water in order to avoid product is in the suds.
The present invention is by the improvement on the above Technology, the chemical manganese bioxide of being produced not only has Manganse Dioxide utilization ratio height, liquid absorption is big, the battery recovery performance is strong, anti-leakage waits all advantages of chemical manganese bioxide well, its short-circuit current and load voltage and big electric current heavy loading discharge property all are better than electrolytic manganese dioxide, become the high quality raw material of producing alkali manganese type drying battery, its product master content is brought up to 95%-95.5% by original 92%, foreign matter content reduces significantly, it is little to have environmental pollution, facility investment is few, (can go out product in three days) with short production cycle, production cost is low, (because of no ammonia follows compression process, whole process of production need not High Temperature High Pressure to stable and reliable product quality, is easy to control every technic index, be convenient to the operation) etc. advantage, be applicable to the production alkaline Mn cell.
Below to produce chemical manganese bioxide with Manganse Dioxide breeze roasting system manganous sulfate be that example is further described detailed structure of the present invention.
Embodiment
Embodiment one: the method that chemical manganese bioxide is produced in the manganese sulfate monohydrate pyrolysis comprises the steps:
Breeze roasting: get content and be about 60% manganese dioxide powder (fineness 200 orders) and put the roasting of rotation electric furnace, temperature 750-800 ℃, 2 hours time, the roasting of Manganse Dioxide breeze is become manganic oxide (Mn2O3).
Disproportionation: fetch and receive mother liquor 2800kg, content is the dilute sulphuric acid 800kg of 300g/L, the manganic oxide breeze 1200kg (solid-to-liquid ratio 1: 3) that roasting is good is mixed with ore pulp, puts to react between the inherent 92-96 ℃ of temperature of reactor and makes the manganese sulfate solution ore pulp in 60 minutes.
Deironing: with the good manganic oxide breeze of roasting, between temperature 90-96 ℃, evenly join in the manganese sulfate solution ore pulp while stirring, utilize manganic oxide breeze disproportionation reaction to need the vitriolic principle, the manganese sulfate solution pulp PH value is adjusted between the 5-5.5, as iron-free in the solution, get final product press filtration, obtaining product promptly is manganese sulfate solution, adds SDD solution in press filtration, and purpose is removed the heavy metal in the solution.
Manganese sulfate solution is refining: the manganese sulfate solution that will add SDD solution is static to be deposited 72 hours, the various foreign matter contents of sampling analysis solution, and press filtration afterwards up to standard obtains the POV manganese solution of BE ° of 23-24.
The pressure crystallization: the pressure crystallizing pan is provided with tensimeter, thermometer, blow-off valve, safety valve, stirrer 60-65 rev/min, filter on top, bottom filter tap, electrothermal tube, pressing force pot total volume 80% adds the POV manganese solution, heating, after pressure reached 2-5kg, constant voltage was after 1 hour, open filter tap, clear liquid is put.Stop to stir, cut off electrothermal tube power, the opening pressure pot is poured out product, through centrifugal, deposits material-stored pool in again, sampling analysis, qualified after, can enter baking, standard water-content is below 3%.
The dehydration roasting: the dehydration roasting is that the water molecules in manganese sulfate monohydrate (MnSO4.H2O) lattice is removed, be not meant surface water, manganese sulfate monohydrate is put the rotation electric furnace with 550-600 ℃ of temperature roasting 2 hours, make manganous sulfate become canescence and get final product by original white or micro mist redness.
Pyrolysis: the manganous sulfate after will dewatering places the rotation electric furnace, and temperature is controlled between 1000-1400 ℃, and roasting in oxygen-rich air, makes it to become trimanganese tetroxide at 2 hours time.
Redox: the trimanganese tetroxide that pyrolysis obtains is inserted in the 700-850 ℃ of rotation electric furnace again, feeding oxygen level is the oxygen-rich air of 60-50%, roasting in oxygen-rich air, time 2.5-6 hour, the part trimanganese tetroxide is direct oxidation into contains the thick Manganse Dioxide of Manganse Dioxide more than 75%, can reduce oxygenant chloric acid sodium consumption 30%, make the crystalline structure in the manganese dioxide product bring up to 98% by original 75% for the content of " r " type structure, increase micropore, the aperture of product particle, reduce specific surface area, improve the product heavy-current discharge performance; Also have the part trimanganese tetroxide to be transformed into manganic oxide.
Disproportionation. oxidation: disproportionation and oxidation two procedures carry out in same reactor, and Manganse Dioxide nucleus amount when reacting for controlled oxidation improves bulk specific gravity, saves the vitriolic consumption, adopt to divide and feed in raw material for three times, and disproportionation and oxidation hocket; And solid-to-liquid ratio must be controlled at 1 during each disproportionation reaction: 2-3, but when disproportionation reaction is finished after when adding the sodium chlorate oxidation, should prolong solid-to-liquid ratio is reduced to 1 along with the reaction times: in the 1.5-2.5 scope, (be controlled at 24-30m with the specific surface area of reduction product
2/ g scope), improves bulk specific gravity (being controlled in the 1.65-1.75g/ml scope), improve the product fill-up, thereby improve the drying battery discharge capacity.
Disproportionation for the first time: washup slag recycle-water 900kg, dilute sulphuric acid 300kg, manganic oxide powder 600kg, add reactor together and stir, temperature of reaction 92-94 ℃, in 1 hour reaction times, disproportionation finishes for the first time.
Oxidation for the first time: get sodium chlorate 90kg, once drop into 60kg, remaining 30kg visual response temperature adds, because of oxidizing reaction is a thermopositive reaction, when surpassing 95 ℃, temperature stops to feed in raw material, reinforced when being lower than 91 ℃, oxidizing reaction temperature is controlled between 90-96 ℃ 3.1 hours reaction times, manganous sulfate content in the detection reaction solution is strict controlled in below the 10g/L simultaneously, can prevent fully that like this manganic oxide is entrained into product; When acid content in the reaction solution reaches about 70g/L, can carry out second disproportionation, be lower than 60g/L and prolong oxidation time again and make and reach more than the 70g/L.
Disproportionation for the second time: dilute sulphuric acid 100kg, washup slag recycle-water 500kg, manganic oxide powder 300kg add reactor together, treat that temperature is raised to 90 ℃ of timing, react after 30 minutes, can carry out the oxidation second time;
Oxidation for the second time: get sodium chlorate 40kg, at first drop into 20kg, remaining 20kg visual response temperature drops into 4.5 hours reaction times, manganous sulfate content in the detection reaction solution is strict controlled in below the 10g/L simultaneously, can prevent fully that like this manganic oxide is entrained into product; Acid content can be carried out disproportionation for the third time in the reaction solution about 60g/L, is lower than 50g/L and prolongs the reaction times and make acid content reach 60g/L.
Disproportionation for the third time: with diluted acid 100kg, washup recycle-water 500kg, manganic oxide powder 300kg, add reactor together, treat that temperature is raised to 90 ℃ of timing, react after 30 minutes, can carry out oxidation for the third time;
Oxidation for the third time: get sodium chlorate 50kg, at first drop into 20kg, remaining 30kg visual response temperature drops into, thrown timing after the sodium chlorate, 6 hours reaction times, manganous sulfate content in the detection reaction solution is strict controlled in below the 10g/L simultaneously, can prevent fully that like this manganic oxide is entrained into product.
Pickling: content 300g/L diluted acid 1000kg is added pickling tank, add the 200kg clear water again, solid-to-liquid ratio is 1: 1, stir, temperature is controlled at about 98 ℃ reacted 60 minutes, the pickling end, the pickling mother liquor is the same with reaction mother liquor to be reclaimed (take a sample respectively before the reaction and after the reaction and divide plate acid content and manganous sulfate content, the front and back contrast can be found out pickling effect).
Washing: the pickling mother liquor was allocated clear water into by 1: 1 after reclaiming again, put into washing after stirring, treat its heavy put top clear liquid clearly after, put into 85 ℃ of hot water again, stirred 15-20 minute, stop to stir, make it heavy clear, put top clear liquid, put into 75 ℃ of hot water again, sink behind the restir and put top clear liquid clearly, put into 75 ℃ of hot water again ..., repetitive scrubbing is washed neutralization again between the 2.0-2.5 with the washing lotion pH value.
Neutralization: stop to stir, allow its precipitation, put top clear liquid, put into cold water again temperature is transferred to below 40 ℃, can neutralize, add the yellow soda ash neutralization and, be not suitable for alkaline Mn cell to prevent product from carrying ammonium ion secretly without the bicarbonate of ammonia neutralization; The pH value 5-7 that neutralizes, restir 30 minutes, pH value is constant, and neutralization finishes, again with the washing of deionization soft water, the impurity in the planar water in order to avoid product is in the suds; Washed one time restir 10-15 minute, the press filtration oven dry gets final product.
Embodiment two: the method that chemical manganese bioxide is produced in the manganese sulfate monohydrate pyrolysis comprises disproportionation. oxidizing process, get washup slag recycle-water 1500kg, dilute sulphuric acid 300kg during disproportionation for the first time, manganic oxide powder 600kg adds the reactor reaction together; For the second time get washup slag recycle-water 800kg, dilute sulphuric acid 100kg during disproportionation, manganic oxide powder 300kg adds the reactor reaction together; Get washup recycle-water 800kg, diluted acid 100kg, manganic oxide powder 300kg during disproportionation for the third time, add the reactor reaction together.All the other technologies are identical with embodiment one.
The present invention is by the improvement on the above Technology, and the chemical manganese bioxide of being produced becomes the high quality raw material of producing alkali manganese type drying battery, and its product master content is brought up to 95%-95.5% by original 92%, and foreign matter content reduces significantly.
Claims (9)
1. the method for chemical manganese bioxide is produced in a manganese sulfate monohydrate pyrolysis, it comprises that breeze roasting, disproportionation, deironing, manganese sulfate solution are refining, pressure crystallization, dehydration roasting, pyrolysis, redox, disproportionation. processing steps such as oxidizing reaction, pickling, repetitive scrubbing, neutralization, press filtration oven dry, the trimanganese tetroxide that it is characterized in that generating after the pyrolysis is when redox reaction, feeding oxygen level is the oxygen-rich air of 60-50%, and oxidization time is 2.5-6 hour.
2. the method for chemical manganese bioxide is produced in manganese sulfate monohydrate pyrolysis according to claim 1, it is characterized in that at disproportionation. and in the oxidation reaction process, solid-to-liquid ratio must be controlled at 1 during each disproportionation reaction: 2-3.
3. the method for chemical manganese bioxide is produced in manganese sulfate monohydrate pyrolysis according to claim 1 and 2, it is characterized in that after disproportionation reaction is finished, and when adding the sodium chlorate oxidation, should solid-to-liquid ratio be reduced to 1 along with the reaction times prolongation: 1.5-2.5.
4. the method for chemical manganese bioxide is produced in manganese sulfate monohydrate pyrolysis according to claim 1 and 2, it is characterized in that at disproportionation. in the process of oxidizing reaction, when each oxidizer is carried out oxidizing reaction, the reaction times of oxidizing reaction was controlled at 3.1-6 hour, manganous sulfate content in the detection reaction solution is strict controlled in it below 10g/L simultaneously.
5. the method for chemical manganese bioxide is produced in manganese sulfate monohydrate pyrolysis according to claim 3, it is characterized in that at disproportionation. in the process of oxidizing reaction, when each oxidizer is carried out oxidizing reaction, the reaction times of oxidizing reaction was controlled at 3.1-6 hour, manganous sulfate content in the detection reaction solution is strict controlled in it below 10g/L simultaneously.
6. the method for chemical manganese bioxide is produced in manganese sulfate monohydrate pyrolysis according to claim 1 and 2, it is characterized in that when repetitive scrubbing, washing lotion P H value is washed between the 2.0-2.5 neutralize with yellow soda ash again; After neutralization finishes, with the washing of deionization soft water.
7. the method for chemical manganese bioxide is produced in manganese sulfate monohydrate pyrolysis according to claim 3, it is characterized in that when repetitive scrubbing, the washing lotion pH value is washed between the 2.0-2.5 neutralize with yellow soda ash again; After neutralization finishes, with the washing of deionization soft water.
8. the method for chemical manganese bioxide is produced in manganese sulfate monohydrate pyrolysis according to claim 4, it is characterized in that when repetitive scrubbing, the washing lotion pH value is washed between the 2.0-2.5 neutralize with yellow soda ash again; After neutralization finishes, with the washing of deionization soft water.
9. the method for chemical manganese bioxide is produced in manganese sulfate monohydrate pyrolysis according to claim 5, it is characterized in that when repetitive scrubbing, the washing lotion pH value is washed between the 2.0-2.5 neutralize with yellow soda ash again; After neutralization finishes, with the washing of deionization soft water.
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| CN1163414C (en) * | 1999-09-30 | 2004-08-25 | 杜祖德 | Monohydrated mangnese sulfate pyrolysizing process for producing mangness dioxide |
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